DD147497A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The present invention relates to pest control compositions comprising a solid or liquid carrier and novel carboxylic acid esters of the formula I in which R & exp1 !, R & exp2! and R & exp3! are the same or different and are hydrogen, halogen, alkyl or alkenyl of up to 5 carbon atoms; Y is a 3- (2,2-dihalo-vinyl) -2,2-dimethyl-cyclo-propyl radical or a radical of the formula II where R & exp4! unbranched or branched alkyl, alkenyl or alkynyl having up to 4 carbon atoms or an alicyclic radical having from 3 to 7 carbon atoms; R & exp5! Halogen, alkyl or alkoxy having up to 5 carbon atoms, trihalomethyl, cyano or nitro and a is 0 to 3, and Z is a radical of the formula III, wherein X is oxygen, sulfur or -CH & ind2! -; R & exp6 !, R & exp7! and R & exp8! Halogen, alkyl, alkoxy or haloalkyl having up to 5 carbon atoms and b, c and d are 0 to 3, are present as active ingredients.

Description

1 7 207 · * -

O.Z. OO5O / O33548

Pesticides Field of application of the invention

The new pesticides can be used in plant protection, hygiene, storage and veterinary sector for controlling pests, especially insects and arachnids.

The invention relates to pesticides containing new carboxylic acid esters as active ingredients.

Characteristic of the known technical solutions

It is known that 2,2-dimethyl-3- (2 ', 2'-dimethyl-vinyl) -cyclopropanecarboxylic acid esters which contain an ethylenyl radical substituted in the α-position by alkenyl as the alcohol component are insecticidally effective (BE-PS 770 37 ¹ O. Furthermore, from Agr Biol.-Chem known 3_7, 2681 (1973), that the substituted oC in Ste-Settin g at Phenoxybenzylrest by vinyl 2,2-dimethyl-3- (2 ', 2'.. - However, this compound is less effective insecticidally than the ester containing as the alcohol component the unsubstituted 3-phenoxybenzyl radical (Agr. Biol. Chem. , 247-29 (1976)).

Object of the invention

The aim of the invention is the development of pesticides with increased efficacy.

2172

O.Z.OO 50/0335 ^ 8

^Hensens

invention

The invention has for its object to provide new pesticides.

It has been found that pesticides containing the new carboxylic acid esters of the formula I

Y-COO-CH-Z

wherein R, R and R ^ are the same or different and are hydrogen, halogen, alkyl or alkenyl of up to 5 carbon atoms, Y is a 3 ~ (2,2-dihalo-vinyl) -2,2-dimethyl-cyclopropyl radical or a radical the formula

CH-

where R is unbranched or branched alkyl, alkenyl or alkynyl having up to 4 carbon atoms or an alicyclic radical having 3 to 7 carbon atoms, R ^ is halogen, alkyl or alkoxy having up to 5 carbon atoms, trihalomethyl, cyano or nitro and a O to, and Z is a radical of the formula

or

7207

- 3 - O.Z.0050 / 033548

wherein X is oxygen, sulfur or -CH ₀ -, R, R and R are halogen, alkyl, alkoxy or haloalkyl having up to 5 carbon atoms and b, c and d are 0 to 3,

Control pests, especially insects and arachnids more effective than known pesticides.

In the formula I, Y is a 3- (2,2-dihalo-vinyl) -2,2-dimethyl-cyclopropyl radical, for example the 3α (2,2-dichlorovinyl) -2,2-dimethyl-cyclopropyl radical 3- (2,2-dibromovinyl) -2,2-dimethylcyclopropyl or the 3- (2,2-difluorovinyl) -2,2-dimethyl-cyclopropyl radical, or a radical of the formula

up to three identical or different substituents

5 p

R can wear on the phenyl ring. As substituents R come

2Q halogen, for example fluorine, chlorine or bromine, trihalomethyl, for example trifluoromethyl, trichloromethyl, cyano, nitro or unbranched or branched alkyl or alkoxy groups having up to 5 carbon atoms, for example methyl, methoxy, ethyl, ethoxy, n-propyl,

Ε Isopropyl, tert-butyl, isobutyl, pentyl, isopentyl, n-propoxy, n-butoxy, isopropoxy, sec-butoxy, isobutoxy, n-pentoxy, isopentoxy, into consideration.

h R can be unbranched or branched alkyl, alkenyl or alkynyl having up to k carbon atoms, for example

Methyl, ethyl, isopropyl, tert-butyl, 'isobutyl, allyl, isopropenyl, propargyl, or an alicyclic radical having 3 to 7 carbon atoms, for example cyclopropyl or cyclohexyl.

Z in formula I is radicals of the formulas

7 2 O 7

O.Z.0050 / 0335 ^ 8

R '

or

in which X is oxygen, sulfur or a methylene group, for example 3-phenoxyphenyl, 5-benzyl-uryl- (3), 5-phenoxy-furyl- (3), 5-phenoxy-furyl- (2) , 3-Benzylphenyl, 3-phenylthiophenyl, 5-phenylthio-furyl- (3). The phenyl rings in the formulas of the radicals for Z may optionally each carry up to three identical or different substituents. Suitable substituents R, R and R are halogen, for example fluorine, chlorine, bromine, unbranched or branched alkyl, alkoxy or haloalkyl groups having up to 5 carbon atoms, for example methyl, ethyl, propyl, isopropyl, n-butyl, tert. Butyl, isobutyl, isomeric pentyl, methoxy, ethoxy, n-propoxy, isopropoxy, isomeric butoxy or pentoxy, trifluoromethyl, trichloromethyl, into consideration.

R,

R and

in formula I independently of one another are hydrogen, halogen, such as fluorine, chlorine, bromine, unbranched or branched alkyl or alkenyl having up to 5 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, n-pentyl , Isopentyl, vinyl, allyl, n-propenyl, isopropenyl, n-butenyl radicals, n-pentenyl radicals, 1-methyl-n-propenyl radicals, 1-methyl-n-butenyl radicals,.

Preferred compounds of the formula I are those in which Y is a 3- (2,2-dihalogenovinyl) -2,2-dimethylcyclopropyl radical or a phenyl radical which is monosubstituted by fluorine, chlorine, bromine or alkoxy having up to 5 carbon atoms ( 7 "isopropylbenzyl, Z is the 3-Pn" enoxyphenyl radical or the 5-benzyl-furyl (3) radical and R, R and R are hydrogen or fluorine.

- 5 - O.Z. OO5O / O3354

Examples of esters of formula I are 2,2-dimethyl-3- (2 ', 2'-dichlorvinyD-methylcyclohexyl trans - ^(3-ph': enoxy -vinyl-benzyl) ester, 2,2-dimethyl-3 (2 ', 2'-dibroravinyl) -cyclopropylcarboxylic acid (3-phenoxy-c-vinyl-benzyl) ester, 2,2-dimethyl-3- (2', ^2f- difluorovinyl) -cyclopropanecarboxylic acid (3-phenoxy-öC-vinyl-benzyD-ester, 2- (4-chlorophenyl) -isovaleric acid- (3-phenoxy-o6-vinyl-benzyl) -ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid (5-benzyl- <X, -vinyl-furfuryl-3) ester, 2,2-dimethyl-3- (2 ', ^2f- difluorovinyl) -cyclopropanecarboxylic acid [5 -benzyl-oC ~ (2-met-hy-1-propen-1-yl) -furfuryl-3] -ester, 2 _J 2 »dimethyl-3- (2 '» 2'-difluorovinyl) -cyclopropanecarboxylic acid [3-phenoxy -c6- (2-methyl-propen-1-yl) -benzyl] -ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -eyopropanecarboxylic acid - (5-benzyl-o6-isopropenyl) furfuryl-3) ester, 2,2-dimethyl-3-bis (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid [5-benzyl-oC-c-buten-1-yl) -furfuryl-3] - ester, 2,2-dimethyl-3- (2 ', 2'-di f luorvinyl) -Cyclopropanecarboxylic acid [3 ~ pnenoxy- <X (n-propen-l-yl) -benzyl] ester, 2,2-dimethyl-3- (2 ^f, 2 ^f -difluorvinyD-cyclopropane carboxylic acid C 3 ~ (4-chlorophenoxy) ~ -O- (1-chloropropen-1-yl) -benzyl] ester, 2,2-dimethyl-3 ~ (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid [3- phenoxy -06- (n-buten-1-yl) -benzyl] -ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid [5-benzyl-c] r ( 2,2-dichlorovinyl) -furfuryl-3] -ester, 2,2-dimethyl-3- (2 ', 2 · -dibromovinyl) -cyclopropanecarboxylic acid - (3-phenoxy-o-isopropenyl-benzyl-D-ester, 2,2-Dimethyl-3- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid C 3 -phenoxy-X- (2,2-dichlorovinyl) -benzylj-ester, 2,2-dimethyl-3-one 2 ^f , 2'-dibromovinyl) -cyclopropanecarboxylic acid [5-benzyl-oc- (n-propen-1-yl) -furfuryl-3] - ester, 2,2-dimethyl-3- (2 ', 2' -dibromovinyl) -cyclopropanecarboxylic acid [5- (4-fluorophenyl) -o / -vinyl-furfüryl-3! -ester, 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) -eyelopropancarboxylic acid ( 3-benzyl-tX-vinylbenzyl) ester, 2- (4-chlorophenyl) ~

^ S -isovaleric acid (3 '',) henylithio - <^ - vinylbenzyl) ester,

- 6 - O.Z. OO5O / O33548

^r 2 ⁽ⁱ 4 ~ chlorophenyl) ~ ~ i8Ovaleriansäure [3-phenoxy-C6 (1-chlorovinyl) -4-fluoro-benzyl] ester, 2- (4-chlorophenyl) isovaleric acid t ~; 3 ™ ( 4-fluorophenoxy) o -vinylbenzyl] ester, 2- (4-chloro or phenyl) isovaleric acid (3-phenoxy-o <-trifluorobutylbenzyl) ester, 2,2- Dimethyl 3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylic acid O-phenoxy-oo-isopropenyl-benzyl) - ester, 2,2-dimethyl-3- (2', 2'-dichlorovinyl-cyclopropanecarboxylone [3- "" phenoxy-o <>"(2,2-dichlorovinyl) benzyl] ester, 2,2-dichloro-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylic acid [5-benzyl] o6 "(n-propen-1-yl) -furfuryl-3] -ester, 2,2-dimethy1-3- (2 ', 2'-dichlorovinyl) -eyopropanecarboxylic acid [5- (4-fluorophenyl) -OCO vinyl furfury1-3] ester, 2,2-dimethyl-3- (2 ', ^2f -dichlorovinyl) -cyclopropanecarboxylic acid (3-benzyl-cx: -vinyl-benzyl) ester, 2,2-dimethyl- 3- (2 ', 2 ¹ -dichlorovinyl) -cyclopropanecarboxylic acid (3-phenylthio (X-vinylbenzyl) ester, 2,2-dimethyl-3- (2', 2'-dichlorovinyl) -cyclopropanecarboxylic acid [3-phenoxy-o6- (1-chlorovinyl) -4-fl uor-benzyl] ester, 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylic acid [3 (4-fluorophenoxy) -c, vinylbenzyl] ester, 2, 2-Dimethyl-3- (2- ^T , 2'-dichloro-vinyl-D-cyclopropanecarboxylic acid (3-phenoxy-3-trifluorovinylbenzyl) ester, 2,2-dichloro-3- (2 ', 2'-dichlorovinyl) - cyclopropanecarboxylic acid [3- (4-chlorophenoxy ) oC- (1-chloro-n-propene-1-yl) -benzyl] -, 2- (4-chlorophenyl) -isovaleric acid [3-phenoxy-c ^: - - (n-propen-1-yl) -benzyl] -ester, 2- (4-chlorophenyl) isovaleric acid [3- (4-chlorophenoxy) ~ c <; - 1-chloropropen-1-yl ) - · benzyl] ester, 2- (4-chlorophenyl) -isovaleric acid [3 ~ phenoxy- ^ 0- (n-buten-1-yl) benzyl] ester, 2- (4-chlorophenyl) - isovaleric acid [5-b.enzyl-06- (2,2-dichlorovinyl) -furfuryl-3] -ester, 2,2-dimethyl- (2 ', 2'-dibromovinyl-D-cyclopropanecarboxylic acid (5-t > enyl-6-vinyl-furfuryl-3) -ester, 2,2-dimethyl- (2 ^! , 2'-dibromovinyl-D-cyclopropanecarboxylic acid - [5-benzyl- 1-oC- (2-methyl-propen-1-yl) -furfury1-3] -ester, 2,2-dimethyl- (2- ^f , 2'-dibromoyl D -cyclopropanecarboxylic acid · - [3-phenoxy-oo- (2-meth ', 1-propen-1-yl) -benzyl] -ester,

7,207 '. , ·

- 7 - O.Z. OO5O / O33548

2,2-Dimethyl- ( ^2f , 2'-dibromo-vinyl) ^{-cyclopropanecarboxylic acid Ί} - (5-benzyl-oc-isopropenyl-furfuryl-3) -ester, 2,2-dimethyl- (2 ¹ , 2 ' -dibromovinyl) -cyclopropanecarboxylic acid [5-benzyl- (n-buten-1-yl) -furfuryl-3] -ester, 2,2-dimethyl- (2 ^t , 2 '- -dibromovinyl) -cyclopropanecarboxylic acid [3 ~ phenoxy-o6- (n-propen-1-yl) -benzyl] -ester, 2,2-dimethyl- (2 ', 2 · -dibromovinyl-1-cyclopropanecarboxylic acid) - f ^ -phenoxy - ^ - (n-butene -1-yl) - benzyl] ester, 2,2-dimethyl- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid 5-benzyl-cc (2,2-dichlorovinyl) -furfuryl-3] -ester, 2 , 2-Dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid (3-phenoxy-o <S-isopropenyl-benzyl) ester, 2,2-dimethyl-3- (2', 2'-difluorovinyl) -cyclopropanecarbonyl-C3-phenoxy-06- (2,2-dichlorovinyl) -benzyl] -ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid - [ 5-benzyl-o6- (n-propen-1-yl) -furfuryl-3] -ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid - [5- (4- fluorophenyl) -5 <^ vinyl-furfuryl-3] -ester, 2,2-dimethyl-3 ~ (2 ', 2'-difluo rvinyl) -eyepropanecarboxylic acid (3-benzyl-o-vinylbenzyl) ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid (3-phenylthio) -vinyl benzyl) - ester, 2,2-dimethyl-3- (2- ^t , 2'-difluorovinyl) -eyopropanecarboxylic acid [3-phenoxy- [ci] (1-chloro-vinyl) -4-fluorobenzyl ] - ester, 2,2-dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid [3- (4-fluorophenoxy) -i> d-vinylbenzyl] ester, 2,2- Dimethyl-3- (2 ', 2'-difluorovinyl) -cyclopropanecarboxylic acid O-phenoxy-trifluorovinyl-benzyl-ester, 2,2-dimethyl-3-bis (2', 2'-dibromovinyl) -cyclopropanecarboxylic acid ( 3-phenylthio-c <: - vinylbenzyl) ester, 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid [3-phenoxy- <XI- (1-chlorovinyl) 4-fluoro-benzyl -] - ester, 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid [3- (4-fluorophenoxy) - o] -vinyl-benzyl] -ester , 2,2-Dimethyl-3- (2 ', 2'-dibromo)

vinyD-cyclopropanecarboxylic acid C 3 -phenoxy-t i-trifluorovinylbenzyl) ester, 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) cyclopropanecarboxylic acid [3- (4-chlorophenoxy) -i -Xr · (1-chloro-n-propene

- 8 - O.Z. OO5O / O33548

-l-yl) -benzyl] ester, 2- (4-chlorophenyl) -isovaleric acid - (5-benzyl-o6-vinyl-furfuryl ~ 3) ester, 2 - (^ -chlorophenyl) - isovaleric acid [ 5 ~ benzyl-c <l · - (2-methyl-propen-1-yl) -furfuryl-3] ester, 2- (4-chlorophenyl) -isovaleric acid - [3-phenoxy-oC- (2-methyl -propen-1-yl) -benzyl] ester, 2- (4-chlorophenyl) -isovaleric acid (5-benzyl-o6-isopropenyl-furfury1-3) ester, 2- (4-chlorophenyl) -isovaleric acid - [5-benzyl-oo- (n-butene-1-yl) -furfuryl-3] -ester, 2,2-di-methyl-3- (2 ', 2'-dihydro-vinyl) -cyclopropanecarboxylic acid 5- - benzyl-oo-vinyl-furfuryl-3) -ester, 2,2-dimethyl-3- (2 », 2 ♦ -. -dichlorovinyl) -cyclopropanecarboxylic acid [5-benzy-l-ö <- (2- -methyl-propen-1-yl) -furfuryl-3] -ester, 2,2-dimethyl-3- (2 ^f , 2 ^l -dichlorovinyl) -cyclopropanecarboxylic acid [3-phenoxy- -06 · (2-methyl -propen-1-yl) -benzyl] ester, 2,2-dimethyl-3- ( ^2f , 2'-dichloro-vinyl-D-cyclopropanecarboxylic acid-CS-benzyl-6-isopropenyl-furfuryl-3) ester, 2 2-Dimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylic acid [5-benzyl-i> d- ( n- - -butene-1-yl) -furfuryl-3] -ester, 2,2-dimethyl-3- (2 ^! 2-dichloro-dichlorocyclopropanecarboxylic acid [3-phenoxy-o <> - (n ~ -propen-1-yl) -benzyl] -ester, 2,2-dimethyl-3- ( ^2f , 2'- dichlorovinyl) -cyclopropanecarboxylic acid C 3-phenoxy - <- - (n-buten-1-yl) - benzyl] ester, 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) -cyclopropanecarboxylic acid [5-benzyl <X- (2 _J 2-dichlorovinyl) -3 -furfuryl-] ester, 2- (4-chlorophenyl) -isovaleriansäure- (3 ~ phenoxy -OC-isopropenyl-benzyl) ester, 2 - (4-chlorophenyl) -isovaleric acid [3-phenoxy-o <i- (2,2-dichloro-vinyl) -benzyl] -ester, 2- (^ i-chlorophenyl) -isovaleric acid [5-benzyl -iX- (n-pr-open-l-yl) -furfuryl-3] -ester, 2- (4-chlorophenyl) -isovaleric acid- [5- (4-f-luprphenyl) -O-vinyl-furfuryl-3 ] ester, 2- (4-chlorophenyl) -isovaleric acid (3-benzyl-c-vinyl-benzyl) ester. It goes without saying that the name of the esters includes all possible isomers.

U /

- 9 - O.Z. OO5O / O33548

The Carbonsäureester of formula I can be converted ^Ί acid halides of the formula II

Y-CO-HaI II, 5 in the

Y has the abovementioned meanings and Hal is halogen, in particular chlorine, in the presence of an acid-binding agent with compounds of the formula III 10

HO-CH-Z _

  T

C = C _x - III, R ^

in which R ¹ , R ² will be held.

12

R, R, R and Z have the meanings given above,

In addition, it is possible, the esters of formula I by reaction of acids of formula IV

Y-COOH IV,

in which Y has the abovementioned meanings, with halides of the formula V

Hal-CH-Z, C = C ^ ₉ V, I ₁ \ r2

12 3 "

in which R, R, R "and Z have the abovementioned meanings and Hal is halogen, in particular chlorine, in the presence of an acid-binding agent

O.Z.0050 / 0335 ^ 8

Further synthetic routes are the reaction of acids of the formula IV with compounds of the formula III in the presence of a water-binding agent and the reaction of alkyl esters of the formula VT

Y-COOR

VI

in which Y has the abovementioned meanings' and R is unbranched or branched alkyl having 1 to 5 carbon atoms, with compounds of the formula III in the presence of a catalyst customary for transesterifications.

The individual reaction paths can be represented by the following reaction equations:

a) Y-CO-HaI

+ HO-CH-Z C = C ^.

acid-binding agent

II

III

b) Y-COOH

IV c) Y-COOH

+ HaI-CH-Z

C = C ^

^RJ

+ HO-CH-Z,

I R- ⁵

C = C ^ «

acid-binding agent

water binding agent

^ I

IV

ΪΙΙ

- 11 - O.Z. 0050/0335 ^ 8

c1) Y-COOR + HO-CH-Z, catalyst

j / R ³ >

C = C ₂

VI III

Suitable acid-binding agents for the synthetic routes a) and b) are organic bases, for example tertiary amines, such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine or pyridine, and also inorganic bases, such as hydroxides, oxides, bicarbonates or carbonates of alkali metals or alkaline earth metals, for example Sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium bicarbonate, potassium carbonate, and alcoholates or hydrides of the alkali metals, for example, sodium hydride or potassium t-butylate, into consideration. The acid-binding agent is used in at least molar amounts, based on the compound of the formula II or V, respectively.

Suitable water-binding agents for the reaction according to reaction equation c) are, for example, dicyclohexylcarbodiimide, inorganic mineral acids, such as sulfuric acid, phosphoric acid, acidic ion exchangers or p-toluenesulfonic acid. The water-binding agent is used in amounts of at least 0.02, advantageously 0.05 to 0.4 mol, based on the existing in deficit reaction component III or IV, respectively.

Suitable catalysts for the transesterification according to reaction equation d) are hydrides or alcoholates of

• Alkali metals, such as sodium hydride, sodium ethylate, and triphenyl sodium. Also suitable are alcoholates of the elements of group IV b of the periodic table, such as titanium tetramethylate, titanium tetraethylate. Per mole of ester of formula VI are suitably 0.02 to 0.4 moles of catalyst

• -zugegeben. , ^Λ j

- 12 - O.Z.0050 / 0335 ^ 8

All manufacturing processes a) to d) are at reaction ^Ί Temperatures in the range between -10 and +150 ⁰ C, under atmospheric or superatmospheric pressure, performed.

To carry out the process, the reaction components of the formulas II and III, IV and V, IV and III and VI and III are preferably employed in equimolar ratios. An excess of one or the other component brings no significant benefits. The implementation is virtually quantitative.

The processes a) to d) are advantageously carried out in the presence of suitable solvents or diluents. As such, virtually all inert organic solvents come into consideration. These include acyclic and cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, alkylated aliphatic and alicyclic carboxylic acid amides such as dimethylformamide, N-methylpyrrolidone, aliphatic and aromatic, optionally chlorinated hydrocarbons such as toluene, xylenes, chloroform, n-hexane, cyclohexane, Chlorobenzene, ketones, such as acetone, methyl ethyl ketone, nitriles, such as acetonitrile, also dimethyl sulfoxide, Hexamethylphosphorsauretriamid. Mixtures of these solvents can also be used.

The process according to reaction equation a) can also be carried out in aqueous solution. As a two-phase reaction, the processes a) and b) can be carried out, it being possible to use, for example, ether, aliphatic and aromatic, optionally chlorinated hydrocarbons, in particular toluene or chloroform, and ketones, such as methyl ethyl ketone, as the water-insoluble organic phase.

Are not in the preparation of the esters of formula I u.

- 13 - Ο.Ζ.ΟΟ5Ο / Ο33548

used uniform, optically active or cis or transisomeric starting materials, the end products are present as mixtures of different optically active isomers and of cis / trans isomers. These isomer mixtures can be separated into the uniform isomers by known methods. The term ester of formula I means both the pure isomers and their mixtures. ·

The starting compounds of formula II are known (GB-PS 1 446 304, US-PS 3,981,903). The compounds of the formula III can be prepared by processes known per se, for example by reacting aldehydes with organometallics or by addition of alkynes to aldehydes with subsequent partial hydrogenation (Houben-Weyl, Methoden der organischen Chemie, Vol. V / lb, p. 775-790, Georg Thieme Verlag, Stuttgart, 1972). Compounds of the formulas IV, V and VI are likewise known and can be prepared by processes known per se (US Pat. No. 3,979,519, US Pat. No. 3,981,903, Pat. No. 801,916, DE-OS No. 2,365,555, US Pat. DE-OS 22 31 312).

The preparation of the esters of the formula I is explained below

 25

la) 3-phenoxy-otvinyl-benzyl alcohol

30 ml of a 1.6 molar solution of vinylmagnesium chloride in tetrahydrofuran are presented in 100 ml of absolute tetrahydrofuran at 0 C. With stirring and exclusion of moisture is added dropwise 9.8 g (0.05 mol) of 3-phenoxybenzaldehyde in 100 ml of absolute tetrahydrofuran to. The mixture is stirred for 3 hours at 25 ⁰ C and decomposes the reaction mixture carefully with a cold. Saturated ammonium chloride solution and a few milligrams.

- 14 - O.Z.OO5O / O33548

Add 10% hydrochloric acid until the precipitate dissolves. Then it is shaken out three times with ether, the combined ether extracts are washed with sodium hydrogen sulfite solution, sodium bicarbonate solution and water, dried over sodium sulfate and concentrated under reduced pressure.

.Gen receives 9.4 g of a yellowish oil, which is pure enough for di.e further implementation

 10

Ber. C 79.6.2 H 6.24 0 I4, I4 Found: C 79.3 H 6.1 0.14.5

Ib) 2,2-Dimethyl-3- (2 ', 2'-dibromovinyl-D-cyclopropane-carboxylic acid (3-phenoxy-o6-vinyl benzyl) ester

To 5.1 g (0.05 mol) of pyridine, 100 ml of absolute ether and 11.4 g (0.05 mol) of 3-phenoxy-oc-vinyl-benzyl alcohol are added at 0 to 5 ° C 15.8 g (0 , 05 mol) 2,2-Dimethy1-3- (2 *, 2'-dibromvinyli-cyclopropanecarboxylic chloride added dropwise with stirring.

After 12 hours of stirring at room temperature, the reaction mixture is filtered off with suction and the filtrate nach ™ each washed with 2N sodium bicarbonate solution, 2N hydrochloric acid and water. After drying over sodium sulfate, the mixture is concentrated under reduced pressure and the resulting oil is purified by column chromatography on silica gel with toluene as eluent.

7907

- 15 - O.2DO5O / O335 ^ 8

An isomer mixture of the formula is obtained

COO-CH

CH = CH ₂

as a yellowish oil with a refraction of nj: ⁸ = 1.5823; Yield: 3 g.

Example 2

a), 3-Phenoxy- (c <6-trifluorovinyl) -benzyl alcohol

In 100 ml of absolute ether 19.32 g (0.12 mol) of l-bromo-l, 2,2-trifluoroethene are gassed at -73 ° C. While flushing with nitrogen, 66.6 ml of a 1.5N butyllithium solution in η-hexane are added dropwise at this temperature. A solution of 19.8 g (0.1 mol) of m-phenoxybenzaldehyde in 100 ml of absolute ether is then added dropwise to this reaction mixture after 30 minutes. After the reaction mixture has warmed to room temperature, it is hydrolyzed with a saturated ammonium chloride solution and dilute hydrochloric acid. The ether phase is separated, washed with a solution of sodium bicarbonate and water, dried and concentrated. This gives 26 g of a dark red oil, which is pure enough for further reactions. '

A small amount is purified on a silica gel column with cyclohexane / acetone (85/15). Isolate a reddish oil with a refraction of η ^J = 1.5442.

- 16 - O.Z.0050 / 033548

b) 2,2-Dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropane-carboxylic acid [3-phenoxy- (c-trifluorovinyl) -benzyl] -ester

I ^ g (0.05 mol) of 3-phenoxy- (oc ~ trifluorovinyl) -benzyl alcohol in 150 ml of absolute ether and 5> 6 g (0.06 mol) of y ^ -picoline are introduced at 0 to 5 ⁰ C. A solution of 11.5 g (0.05 mol) of 2,2-di-methyl-3 "(2 ', 2'-dichlorovinyl) -cyclopropanecarbonyl chloride in 20 ml of absolute ether is slowly added dropwise Room temperature, filtered and washed with 2N hydrochloric acid, 2N sodium bicarbonate solution and water, dried over sodium sulfate and concentrated under reduced pressure, the resulting oil is purified over silica gel column with cyclohexane / acetone (85/15) as eluent; , 2 g; njjp = 1.5390.

Example 3 a) 2-Benzyl- (0-vinyl) -benzyl alcohol

30 ml of a 1.6 molar solution of Viny! Magnesium chloride in tetrahydrofuran are initially charged at 0 ° C. in 100 ml of absolute tetrahydrofuran. While stirring and. Exclusion of moisture is added dropwise 9.8 g (0.05 mol) of 2-benzylbenzaldehyde in 100 ml of absolute tetrahydrofuran. The mixture is stirred for 3 hours at 25 ° C. and the reaction mixture is carefully decomposed with a cold saturated ammonium chloride solution and a few milliliters of 10% strength hydrochloric acid until the precipitate dissolves. Then it is shaken out three times with ether, the combined ether phases washed with sodium bisulfite solution, sodium hydrogen carbonate solution and water, dried over sodium sulfate and placed under

Concentrated under reduced pressure to give 9 g of a

- 17 - O.Z. 0050/0335 ^ 8

yellowish oil, for further reactions

21 is pure enough; n _D = 1.5855.

b) 2,2-Dimethyl-3- (2 ', 2 ^L -dichlorovinyl) -cyclopropanecarboxylic acid [2-benzyl (C'-vinyl) benzyl] ester

To 4.6 g (0.05 mol) of Y'-picoline, 100 ml of absolute ether and 8.5 g (0.38 mol) of 2-benzyl (ft-vinyl) benzyl alcohol are added at 0 to 5 ° C 91 g (0.04 mol) of 2,2-dimethyl-3- (2 ', 2 · dichloro) -cyclopropanecarboxylic chloride are added dropwise with stirring. After 12 hours of stirring at 25 ° C, the reaction mixture is filtered off with suction and the filtrate washed successively with a 2N sodium bicarbonate solution, 2N hydrochloric acid and water. After drying over sodium sulfate is concentrated under reduced pressure and the resulting oil purified by column chromatography on silica gel with'Toluol as EIu-tion agent.

This gives 10.3 g of an isomeric mixture of the formula

as a yellowish oil; nj: · ¹ = 1.5678

Example 30

a) 2-Benzyl- (O (T-trifluorovinyl) benzyl alcohol

In 100 ml absol. Ether are at -78 ⁰ C 19,32 g (0.12 mol) of l-bromo-l, 2,2-trifluoroethane gassed. Under nitrogen flushing, it is added dropwise at the same time

-IS - O. Z. OO5O / O33548

this temperature in several portions 66.6 ml of a l, 5n ButyllithiumlÖsung in η-hexane and 19> 6 g (0.1 mol) of 2 ^: ^ benzyl-benzaldehyde in 100 ml of absolute ether to. It is allowed to rise slowly to room temperature and hydrolyzed with a saturated ammonium chloride solution and dilute hydrochloric acid. The ether phase is separated, washed with a 2N sodium bicarbonate solution and water, dried and concentrated *

The obtained 26.7 g of a dark red oil are pure enough for further reactions.

A small amount is purified on a silica gel column with cyclohexane / acetone = 85/15. A reddish oil is isolated with a refraction of n ^ 3 = 1.5388.

b) 2,2-Dimethyl-3- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid [2-benzyl- (oC-trifluorovinyl) -benzyl] -ester

11.1 g (0.04 mol) of 2-benzyl (oc-trifluorovinyl) benzyl alcohol in 100 ml absol. Ether and 4.6 g (0.05 mol) of fc-picoline are presented at 0 to 5 ° C. A solution of 19.0 g (0.05% WoI) of 2,2-dimethyl-3- (2 ', 2'-dibromovinyl) -cyclopropanecarboxylic acid chloride in 20 ml of absolute ether is slowly added dropwise. The mixture is left to stir overnight at room temperature , filtered and washed the ether solution with 2N hydrochloric acid, 2N sodium bicarbonate. and water, dried over sodium sulfate and concentrated under reduced pressure. The resulting oil is purified over a silica gel column with cyclohexane / acetone = 85/15 as eluent.

O.Z. OO5O / O33548

10.4 g of an oil of the formula are obtained

br

as a mixture of isomers with a refraction of n ^ ¹ = 1.5561.

Analogously, the following compounds can be prepared:

O.23O5O / O33548

Y-COO-CH-Z CH = CH,

No.

10

13

Cl Cl

20 9 cl

11

12 cl

Ό '

• ο-

23

= 1.5628

23

= 1.5595

ng * = 1.5655 25

= 1.5603

η ²³ _D = 1.5630

η ²³ = 1.5621

η ²¹ = 1.5672

η ²¹ = 1.5721

²¹ = 1.5810

2 1 7 P07

Ο.2ΡΟ5Ο / Ο33548

y-co-CH-z C = Cr ¹

Y- K R ¹ R ² R ³

19 Ci PP Pn ²⁵ = 1.5 ^ 22 FP P n ²² = 1.5515

PF Pn ²³ = 1.5353

PF Pn ²³ = 1.5351 HPF n ²² = 1.5553 PP Fn ²² = 1.5320

br

20 ) =

br

br

br

H F

n ²²

= 1.5626

FP Fn ²² = 1.5 ^ 52

Cl

Cl

HF Pn ²³ = 1.5572 "

- 22 - O.2DO5O / O33548

^P No. YZR ¹ R ² R ³

PP Fn ²² = 1.5426 PP Pn ²² = 1.5223

Cl 23 Cl Cl 24 Cl

The compositions according to the invention are suitable for effectively controlling pests of the class of insects and arachnids.

Among the harmful insects belonging to the order of butterflies (Lepldoptera) for example Plutella rnaculipennis' (cabbage), Leucoptera coffeella (coffee moth), Hyponorneuta malinellus (apple tree moth), Argyresthia conjugella (apple moth), Sitotroga cerealella (cereal moth), Phthorimaea operculella (potato moth) , Capua reticulana (apple peel winder), Sparganothis pilleriana (crabworm), Cacoecia murinana (fireworm winder), Tortrix viridana (oak winder), CIysia ambiguella (haywurner and Sauerwurin), Evetria buoliana (pine worm), Polychrosis botrana (grapevine moth), Cydia pomonella (Fruit moth), Laspeyresia molesta (peach driller), Laspeyresia funebrana (plum moth), Ostrinia nubilalis (corn borer), Loxostege sticticalls. (Turnip gurnard), Ephestia kuehniella (flour moth), Chilo suppressalis · (rice stem drill), Galleria Mellonella (wax moth), Malacosoma neustria (marigold spinner), Dendrolimus pini (pine spinner), Thaumatopoea pityocampa (pine processionary moth), Phalera bucephala- (moonspot), Cheimatobia brumata (Little Prostspanner), Hibernia defollaria (Great

- 23 - O.Z. 0050/033548

Frostbite), Bupalus piniarus (pine tree), Hyphantria cunea (white bear moth), Agrotis segetum (winter seed), Agrotis yp'silon (Ypsiloneule), Barathra brassicae (coalleaf), Cirphis unipuncta (armyworm), Prodenia litura (cotton bead), Laphygma exigua (Beet armyworm), Panolis flammea (Forleule), Earias lnsulana (Cotton bollworm), Plusia gamma (Gammaeule), Alabama argillacea (Cotton leaf worm), Lymantria dispar (Sponge spinner), Lyrnantria monacha (Nun), Pieris brassicae (Cabbage white), Aporia crataegi (Baumweißling);

from the order of beetles (Coleoptera) for example Blitophaga undata (Black beet beetle), Melanotus communis (wire worm), Limonius californicus (wire worm), Agriotes llneatus (seed fast beetle), Agricotes obscurus (humus fast beetle), Agrllus sinuatus (pear tree beetle), Meligethes aeneus (Colza beetle), Atomaria lineäris (moss budworm), Epilachna varicestris (Mexican bean beetle), Phyllopertha horticola (Juniper beetle), Poplllia japonica (Japanese beetle), Melolontha melolontha (field beetle), Melolontha hippocastani (woodland beetle), Amphimallus solstitialis (weevil), Crioceris asparagi ( Asparagus chickens), Lema rnelanopus (corncob), Leptinotarsa decemlineata (potato beetle), Phaedon cochleariae (horseradish leaf beetle), Phyllotreta nemorurn (Kohlerdfloh), Chaetocnema tibialis (beetle beetle), Phylloides chrysocephala (rape flea beetle), Diaörotica 12-punctata (southern corn rootworm ), Cassida nebulosa (Misty Beetle), Bruchu s lenti.s (lentil beetle), Bruchus rufimanus (horse bean beetle), Bruchus pisorum (pea beetle), Sitona lineatus (line leaf rag beetle), Otiorrhynchus sulcatus (ragwort), Otiorrhynchus ovatus (strawberry root loafer), Hylobies abietis (large brown weevil), Byctiscus betulae (Grapevine), Anthonomus pomorum (apple blossom stingray), Anthonomus j'randis (capsule beetle), Ceuthorrhynchus

- 24 - o.Z. OO5O / O33548

^r assimilis (Kohlschotenrüßler), Ceuthorrhynchus napi (Large * Kohltriebrüßler), Sitophilus granaria (grain weevils), Anisandrus dispar (Unequal wood bark beetle), Ips typographies (printer), Blastophagus plnlperda (Gefruchter wall Gardener);

from the order of the Diptera for example Mayetiola destructor- (Hessen fly), Dasyneura brassicae (Kohlschoten-Gallmücke), Contarinia tritici (yellow wheat gum mosquito), Haplodiplosis equestris (saddle mosquito), Tipula paludosa (meadow snake), Tipula oleracea (Kohlschnake ), Dacus cucurbitae (melon fly), Dacus oleae (olive fly), Ceratitis capitata (Mediterranean fruit fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletis pomonella (apple), Anastrepha ludens (Mexican fruit fly), Oscinella frit (frit fly), Phorbia coarctata ( Fallow fly), Phorbia antiqua (onion fly), Phorbia brassicae (small cabbage fly), Pegornya hyoscyaml (turnip fly), Musca domestlca (housefly);

from the Hymenoptera order, for example, Athalia rosae (beetroot sawfly), Hoplocampa minuta (plum sawdust), Monomorium pharaonis (pharaoh ant), Solenopsis geminata (fire ant), atta sexdens (leaf-cutting ant);

from the order of the bugs (Heteroptera), for example, Nezara viridula (green rice bug), Eurygaster integriceps (Asian cereal bug), Blissus leucopterus (Chinch bug), Dysdercus cingulatus (Kapok bug), Dysdercus intermedius (cotton bug), Piesma quadrata (beet bug), Lygus pratensis (Common meadow bug);

- 25 - O.Z. OO5O / O33548

'"from the order of the plant sucker (Homoptera), for example, Perkinsiella saccharicida (sugar cane cicada), NiIaparvata lugens (brown cicada), Empoasca fabae (potato), Psylla mali (apple leaf aspirator), Psylla piri (Pirnklatttsauger), Trialeurodes vaporariorum (white fly), Aphis fabae (black bean louse), Aphis pomi (green apple, louse), Aphis sambuci (elderberry aphid), Aphidula nastrutii - (Xanthorrhoid aphid), Cerosipha gossypii (cucumber aphid), Sappaphis mali (rosy apple louse), Sappaphis mala (floury pear aphid), Dysphls radlcola (floury apple louse), 3rachycaudus cardui (large plum aphid), Brevicoryne'brassicae (cabbage aphid), Phorodon humull (hops aphid), Rhopalomyzus ascalonicus (onion louse), Myzodes persicae (green peach louse), Myzus cerasi (black sour cherry louse), Dysaulacorthum pseudosolani (spotted Kartoffellaus), Acyrthosiphon onobrychis (Green pea louse), Macrosiphon rasae (Large rose aphid), Megoura viciae (Wicke nlaus), Schizoneura lanuginosa (pear aphid), Pemphigus bursarius (lettuce root louse), Dreyfusia nordmannianae (fir branch louse), Dreyfusia piceae (white fir stem louse), Adelges laricis (red Fichtengallen louse), Viteus vitifolii (phylloxera);

from the order of termites (Isoptera), for example, Reticulitermes lucifugus, Termes natalensis, · Caloternaes flavicollis, Leucotermes flavipes;

from the order of the Geradflügler (Orthoptera), for example, Porficula auricularia (common earwig), Acheta domestica (crickets), Gryllotalpa gryllotalpa (mole cricket), Tachycines asynamorus (Greenhouse Cricket), Locusta migratoria (migratory locust), Stauronotus maroccanus (Moroccan migratory locust), Schistocerca peregrina (Wandering Grasshopper), Nomadacris septemfasciata (Wanderheuschrelo.

ke), 'Melanoplus spretus (Rock Mountain Locust), Melano-

- 26 - O.Z. 0050/033543

"" plus fernur-s-rubrum (red-legged grasshopper), Blatta orientalis (cockroach), Blattella germanica (German cockroach), Periplaneta americana (American cockroach), Blabera gigantea (giant cockroach)

 5

Mites and ticks (Acarina), for example, belong to the class of arachnoids.Ixodes ricinus (wood buck), Ornithodorus raoubata, Amblyomma americanum, Dermacentor silvarum, Boophilus microplus, Tetranychus telarius, Tetranychus atlanticus, Tetranychus pacificus, Paratetranychus pilosus, Bryobia praetiosa.

The compounds of the invention can be used successfully as pest control agents in crop protection and in the hygiene, storage and veterinary sector.

The active compounds can be used as such, in the form of their formulations or the applications thereof, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

- 27 -. O.Z. OO5O / O33548

For the preparation of directly sprayable solutions, emulsions ¹ NEN, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or tierisehen origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene , Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water into consideration.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

As surface-active substances are alkali metal, alkaline earth metal, ammonium salts of lignosulfonic acid, Naphthalinsulfonsäurej · phenolsulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali and alkaline earth salts of dibutylnaphthalenesulfonic acid, Lauryläthersulfat, fatty alcohol sulfates, fatty alkali and alkaline earth salts, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulphate and fatty alcohol glycol ethers, condensation products of sulphonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene and naphthalene, respectively

- 28 - O.Z. OO5O / O3354 8

acids with phenol and formaldehyde, Polyoxyäthylenoc- ⁿ tylphenoläther, ethoxylated isooctylphenol, octylphenol _s Nonylphenon, alkylphenol polyglycol ether, Tributylphenylpolyglykoläther, Alkylarylpolyätheralkohole, isotridecyl alcohol, Fettalkoholäthylenoxid condensates, ethoxylated castor oil, Polyoxyäthylenalkyläther, ethoxylated polyoxypropylene, Laurylalkoholpolyglykolätheracetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be prepared by binding the active compounds to solid carriers. Solid carriers are e.g. Mineral earths such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations in general contain between 0.1 and 95 wt.% Of active ingredient by weight, preferably between 0.5 and 90.%. ,

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10 %, preferably between 0.01 and 1 %.

1 7 207

- 29 - O.Z. 0050/033548

TThe active ingredients can also be used successfully in the ultra-low-Vo * = "lume process (ULV), it being possible weight formulations over 95.% Of active ingredient or nearly pure active ingredient without additives.

Examples of formulations are:

I. 3 parts by weight of 2,2-dimethyl-3- (2 ^!, 2'-dibromovinyl) - cyclopropanecarboxylic 3-phenoxy-oo-vinyl-benzyl) - ester are intimately mixed with 97 parts by weight of finely divided kaolin. This gives a dust containing 3% by weight of the active compound.

II. 30 parts by weight of 3'-phenoxy-oC'-vinyl-benzyl-oc-isopropyl-4-chlorophenylacetate are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which has been sprayed onto the surface of this silica gel. This gives a preparation of the active substance with good adhesion.

III. 20 parts by weight of 5 ^t -Benzyl-oc'-vinyl-furyl-3 '-methyl- oG-isopropyl-4-chlorophenyl acetate are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide 1 mole of oleoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to give an 'aqueous dispersion containing -0.02 weight percent of the active ingredient.

\

- 30 - o.Z.0050 / 0335 ^ 8

¹ IV. 20'Gew.ichtsteile 2,2-dimethyl-3- (2 ', 2'-dichlorovinyl) -. • »-Cyclopropanecarboxylic [3 ~ phenoxy (C <-trifluorovinyl) - benzyl] ester are dissolved in a mixture consisting of ^ O parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of ^ O moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 weight percent of the active ingredient.

Oils of various types, herbicides, fungicides, other insecticides, bactericides, if appropriate also only immediately before use (tank mix), may be added to the compositions according to the invention.These compositions can be added to the compositions according to the invention in a weight ratio of 1: to 10: 1 ,

For example, the following may be admixed: l, 2-dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene + 1,2-dichloropropane, 1,2-dibromoethane, 2 sec-butyl -phenyl-N-methylcarbamate, o-chlorophenyl-N-methylcarbamate, 3-isopropyl-5-niethylphenyl-N-methylcarbamate, o-isopropoxyphenyl-N-methylcarbamate, 3,5-dimethyl-1-methylmercapto-phenyl-N -methylcarbamate, ⁱ l -dimethylamino-3,5-xylyl-N-methylcarbamate, 2- (1,3-dioxolan-2-yl) -phenyl-N-methylcarbamate., 1-Naphthyl-N-methylcarbamate, 2,3 Dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate, 2,2-dimethyl-1,3-benzodioxol-1-yl-1-yl-methylcarbamate, 2-diethylamino-5 ,. 6-dimethyl- ⁱ ) -pyrimidinyl-dimethylcarbamate, 2-methyl-2- (methylthio) -propionaldehyde-O-methylcarbamoyl-1-oxime, S-methyl-N - [(methylcarbamoyl) -oxy] -thio-acetimidate, methyl-N ^1, N ¹ -dimethyl-N - [(methylcarbamoyl) oxyl-l-thiooxamidatj N- (2-methyl - ^ - chloro-phenyl) -N ', N ^f "dimethylformamidine, Tetrachlorthiol- (2,6-difluoro benzoyl) -3- ( ^J ) -chlorophenyl) -urea ^ j

- 31 - O.Z.Oo.50 / 033548

OjO-dimethyl-O-Cp-nitrophenyl-phosphorothioate _s 0,0-diethyl--- ^O- (p-nitrophenyl) -phosphorothioate, O-ethyl-0- (p-nitrophenyl) -phenyl-phosphonothioate, O, O- Dimethyl 0- (3-methyl-4-nitrophenyl) phosphorothioate, 0,0-diethyl-0- (2,4-dichlorophenyl) phosphorothioate, O-ethyl-0- (2,4-dichlorophenyl) -phenyl phosphonothioate, 0,0-dimethyl-O- ( 2, k , 5-trichlorophenyl) ·; , phosphorothioate, O-ethyl-0- (2,4,5-trichlorophenyl) -ethyl-phosphonothioate, 0,0-nimethyl-O- (4-bromo-2,5-dichlorophenyl) -phosphorothioate, 0.0 dimethyl-0- (2,5-dichloro-4-j odphenyl) - phosphorothioate, 0,0-dimethyl-0- (3-methyl-l ^{i-methylthiophenyl)} phosphorothioate, O-ethyl-O- (3 -methyl-4-methylthiophenyl) -isopropyl-phosphoramidate, 0,0-diathyl-0- [p- (methylsulfinyl) -phenyl] -phosphorothioate, O-ethyl-S-phenyl-ethyl-phosphonodithioate, 0,0-diethyl-C 2-chloro-l- (2, ⁱ i-dichlorophenyl) - -vinylj-phosphate, 0,0-dimethyl - [- 2-chloro-l- (2,4,5-trichlorophenyl)] -vinyl-phosphate 0 , 0-dimethyl-S- (1-phenyl) -ethyl acetate-phosphorodithioate, bis (dimethylamino) -fluorophosphine oxide, octamethyl-pyrophosphoramide, 0,0,0,0-tetraethyldithio-pyrophosphate, S-chloromethyl-O, O- diethyl-phosphorodithioate, O-ethyl-S, S-dipropyl-phosphorodithioate, 0,0-dimethyl-0-2,2-dichloro-vinyl-phosphate, O, O-dimethyl-1,2-dibromo-2,2-dichloroethyl phosphate, 0, 0-dimethyl-2,2,2-trichloro-1-hydroxy-ethylphosphonate, OjO-dimethyl-S-Cl 2 -biscarboxylethoxy ethyl (I)] phosphorodithioate, 0,0-dimethyl-O- (1-ethyl-2-carbmethoxy-vinyl) -phosphate, 0,0-dimethyl-S- (N-methyl-carbamoyl-methyl) -phosphordithioate , 0,0-Dimethyl-S- (N-methylcarbamoyl-ethyl) -phosphorothioate, 0,0-dimethyl-S-CN-methoxyethyl-carbamoyl-methyl-d-phosphorodithioate, 0,0-dimethyl-S- (N-Formyl-N-methyl-carbamoylmethyl-phosphorodithioate, O-dimethyl-O- [1-methyl-2- (methyl-carbamoyl) -vinyl] -phosphate, O-dimethyl-O - [(1 -methyl-2-dimethylcarbamoyl) -vinyl] -phosphate, 0,0-dimethyl-0 - [(1-methyl-2-chloro-2-diethylcarbamoyl) -vinyl] -phosphate, 0,0-diethyl-S- (ethylthio-ethyl) phosphorodithioate, 0.0-diethyl-SC (p-chlorophenylthio) -methyl] phosphorodithioate, OjO-dimethyl-SC ^ -

- 32 - O.Z. OO5O / O33548

^r * -ethylthioethyl) -phosphorothioate, O, O-dimethyl-S- (2-ethyl-thioethyl) -phosphordithioate, 0,0-dimethyl-S - (2-ethylsulfinyl-ethyl) -phosphorothioate, 0,0- diethyl-S- (2-äthylthio- ethyl) phosphorodithioate, O, O-diethyl-S- (2-ethyl äthylsulfinyl-) phosphorothioate, 0,0-diethyl-thiophosphoryliminophenyl-acetonitrile, 0 _s 0-diethyl- S- (2-chloro-1-phthalimidoethyl) phosphorodithioate, 0,0-diethyl-S- [6-chloro-benzoxazolone- (2) -yl (3)] -methyldithiophosphate, 0,0-dimethyl-S- [2-methoxy] -1,3,3-thiadiazol-5 - [(1H-onyl-C 1) -methyl] -phosphordithioate, 0,0-diethyl-O- [3,5,6-trichloropyridyl- (2)] - phosphorothioate, 0,0-diethyl-0 ~ (2-pyrazinyl) -phosphorothioate, 0,0-diethyl-O- [2-isopropyl-4-methyl-pyrimidinyl (6)] -phosphorothioate, 0 , 0-diethyl-0- [2- (diethylamino) ^-6-methyl-i t-pyrimidinyl] '- -thionophosphat, 0,0-dimethyl-S- (4-oxo-l, 2,3-benzotriazin- - 3 - [^ H] -yl-ethyl) phosphorodithioate, 0,0-dimethyl-S - [(4,6-diamino-1,3,5-triazin-2-yl) -methyl] -phosphorodithioate, 0 , 0-diethyl (l-phenyl-l, 2,4-triazol-3-y l) -thionophosphate, O, S-dimethylphosphoramidothioate, OjS-dimethyl-N-acetylphosphoramidothioate, / ^ hexachlorocyclohexane, 1,1-di- (p-methoxyphenyl) -2,2,2 trichloroethane, 6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-π-lethano-2,4,3-benzodioxa-thiepine 3-oxide, pyrethrins, DL-2-allyl-3-ethylcyclopentene- (2) -one- (1) -yl- (4) -dL-cis, trans-chrysanthemate, 5-benzyl-furyl- 3) -methyl-DL-cis, trans-chrysanthemate, 3-phenoxybenzyl (+ _) - cis, trans-2,2-dimethyl-3 ~ (2,2-dichlorovinyl) -cyclopropanecarboxylate, c <rCyano- 3-phenoxybenzyl (+ _) - cis, trans-2,2-dimethy1-3- (2,2-dichlorovinyl) -cyclopropanecarboxylate, (s) -oc-cyano-3-phenoxybenzyl-cis (1R, 3R) - 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropanecarboxylate, 3,4,5,6-tetrahydrophthalimidoethyl-DL-cis, trans-chrysanthemate, 2-methyl. -5- (2-propynyl) -3-furylmethyl-chrysanthemate, ^ -cyano-3-phenoxybenzyl-o-1-isopropyl-4-chlorophenylacetate. ''

* ^l

With particular advantage, compounds of the formula I are also combined with substances which have a synergistic effect.

- 33 - O.Z. OO5O / O33548

"see or exert enhancing effect on pyrethroids. ^Ί Examples of such compounds include: piperonyl butoxide, propynyl, and Propinylcarbamate Propinylphosphonate, 2- (3>4-Methylendi'oxyphenoxy) -3, 6,9-trioxaundecane, SjSjS-Tributylphosphorotrithioate, 1 , 2-methylenedioxy-4- (2- (octylsulfonyl) -propyl) -benzene, 1-n-dodecyl-imidazole, 1- (1,5,9-trimethyldecyl) -imidazole, 1- [2-chloro-2- ( 4-fluorophenyl) -ethyl] -l, 2,4-triazole, 1- (2-phenyl-ethyl) -l, 2,4-triazole, 1- (2-chloro-2-phenyl-ethyl) - l, 2,4-triazole, 1- (3-phenyl-n-propyl) -1, 2,4-triazole.

embodiments

The following examples demonstrate the biological effect of the new agents. Comparative agent is 2,2-dimethyl-3- (2 ¹ , 2'-dimethylvinyl) -cyclopropanecarboxylic acid (3-phenoxybenzyl) ester (Agr. Biol. Chem 21 »2681 (1973)). · The numbering of the active substances corresponds to the production examples

 20

Example A

Contact with houseflies (Musca domestica); Application st

4-day-old Imagines are administered in light COp anesthesia 1 / Ul of the acetone solution of the drug to the ventral abdomen. For this a micrometer syringe is used. 20 test animals each - with the same treatment you bring -in a foil bag (volume about 500 ml).

After 4 hours, the animals are counted supine and graphically determined the LD 50

 35

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Active ingredient No. LD 50

1 0.014 μg / fly

f ' 0,0093 / Ug / Fllege

Comparative agent 0.017 μg / fly

Example B

Contact with cockroaches (Blatta orientalis)

The bottom of a 1 liter preserving jar is treated with the acetone solution of the active ingredient. After evaporation of the solvent, 5 adult cockroaches per glass are placed.

The mortality rate is determined after 48 hours.

Active ingredient No. Active ingredient mortality rate

[mg] [Ji]

1 0.1 100

0.05 80

5 0.1 100

0.05 70

8 0.1 '100

Comparison means 0.1 20

Example C

Feeding and contact on caterpillars of caterpillars -_ (Plutella macülipennis)

Leaves of young cabbage plants are immersed in the aqueous emulsion for 3 seconds and, after briefly draining on a moistened filter, into a petri

- ^

! 7 207 '

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peel. The leaf is then covered with 10 caterpillars of the 4th stage.

After 48 hours to assess the effect. 5 drug no. % Mortality rate at one

Active substance concentration of 0.001 [weight $] 0.0005 [weight *]

5 100

Example D

Contact action on mosquito larvae (Aedes aegypti) 15 200 ml of tap water are mixed with the active ingredient preparation and then populated with 30 to 40 mosquito larvae in the 4th larval stage. The test temperature is

20 ⁰ C. After 24 hours, the effect is determined.

Active ingredient no. Concentration of the active ingredient preparation [ppm] Mortality rate [Ji] 5 0.01 100 5 0,004 about 80 Example E

Contact with ticks (Ornithodorus moubata)

It is tested with ticks in the 3rd instar. To do so, immerse the animals, which are in a paper bag, in the test emulsion for 3 seconds. The bags are free '^

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After 48 hours, the effect on the ticks is assessed.

Drug no. Drug concentration mortality rate

the test emulsion [%]

[Wt.3]

5 0.0001

'. 5 0.00005 '

Claims (1)

O.Z. OO5O / O33548 '' Invention claim A pesticide containing a solid or liquid carrier and 0.1 to 95 wt.% Of a Carbonsäureesters of the formula I Y-COO-CH-Z C = C in the 12 3 R, R and R are the same or different and are hydrogen, halogen, alkyl or alkenyl of up to 5 carbon atoms, Y is a 3- (2,2-dihalo-vinyl) -2,2-dimethyl-cyclopropyl radical or a radical of the formula R: CH- wherein R is straight or branched alkyl, alkenyl or alkynyl having up to 4 carbon atoms or an alicyclic radical having 3 to 7 carbon atoms, R is halogen, alkyl or alkoxy having up to 5 carbon atoms, trihalomethyl, cyano or nitro and a is 0 to 3, and Z is a radical of the formula or - 38 - O.Z.0050 / 0335 ^ 8 where X is acid or sulfur or -CH ₀ -, f \ 7 · ft R, R 'and R are halogen, alkyl, alkoxy or halogen alkyl having up to 5 carbon atoms and b, c and d to 3 mean, stand, as an active ingredient.